8244 Ind. Eng. Chem. Res.

2010, 49, 8244–8247

Isopiestic Study of the Na2CrO4-H2O System at 353.15 K: Prediction of the

Solubility of Na2CrO4 in Aqueous NaOH Solutions
Wei Jin,†,‡ Shili Zheng,*,† Hao Du,† Hongbin Xu,† and Yi Zhang†
National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Key Laboratory of
Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences,
Beijing 100190, People’s Republic of China, and Graduate School of Chinese Academy of Sciences,
Beijing 100049, People’s Republic of China

The osmotic coefficients of the Na2CrO4-H2O system at 353.15 K were determined using isopiestic method
ranging from 0.05 to 7.683 mol · kg-1. The experimental osmotic coefficients were excellently correlated
with Pitzer equation to obtain the interaction parameters, the activity coefficients, and the solubility product
for Na2CrO4. Furthermore, the solubility of Na2CrO4 in NaOH solutions at 353.15 K was predicted using
binary parameters, and the predicted values agree with the experimental data, demonstrating the Pitzer equation
is capable of optimizing the processes for the removal and recovery of sodium chromate in NaOH solutions
at high temperature.

1. Introduction
Chromium-bearing sodium hydroxide solutions are of great
importance in geochemistry,1 environmental treatment,2 and
industrial processes.3,4 In alkaline solutions, Cr exists primarily
as the highly soluble oxyanionic species, CrO42-, which can
lead to significant groundwater contamination as a result of
release from rock or from human activity.5 Among all hazardous
wastes, Cr is the third most frequently cited substance and
among metallic substances is second only to Pb in cited
frequency.6 Consequently, the aqueous chemistry of alkaline
sodium chromate solutions is critical for optimizing numerous
industrial treatments,3,4 such as the basic dissolution of chromite
ore, electroplating, wood pulp production, leather-tanning, and
petroleum refining. Consequently, there is a significant require-
ment for a reliable, comprehensive, internally consistent set of
thermodynamic properties for predicting the phase behavior of
Cr in NaOH solutions.
Considerable research has been carried out on the solubility
diagrams of NaOH-Na2CrO4-H2O systems at various tem-
peratures and concentrations.7,8 To systematically correlate and
predict the solid-liquid equilibrium, it has been necessary to
determine the osmotic and activity coefficients. Due to the great
flexibility and wide applicability, the isopiestic method is
available for aqueous mixed salt solutions. On the basis of the
isopiestic method, abundant experimental osmotic and activity
coefficient data for the NaOH-H2O binary system with
significant temperature and concentration ranges have been
obtained,9,10 while data for the Na2CrO4-H2O system are only
available at 298.15 K.11 However, the unit operations during
chromium-bearing industrial processes mainly focus on the
temperature ranging from 313.15 to 353.15 K,12 addressing the
necessity for the determination of osmotic and activity coef-
ficients for the Na2CrO4-H2O system in such regions for
theoretical and practical reasons. In this regard, the aim of this
study is to measure the osmotic coefficients for the
Na2CrO4-H2O system from m ) 0.05 to 7.683 mol · kg-1 at
353.15 K using our specially designed isopiestic apparatus. The
* To whom correspondence should be addressed. E-mail: slzheng@
home.ipe.ac.cn. Fax: +86-10-62520910.
†
Institute of Process Engineering, Chinese Academy of Sciences.
‡
Graduate School of Chinese Academy of Sciences.
10.1021/ie1011068  2010 American Chemical Society
Published on Web 07/27/2010
experimental data were then correlated with the Pitzer equa-
tion13 to give the reliable parameters. The obtained parameters
were employed and coupled with the parameters of the
NaOH-H2O system previously reported to predict the solubility
of Na2CrO4 in NaOH aqueous solutions at 353.15 K.
2. Experimental Section
In this study, the isopiestic method is used to determine the
osmotic coefficients of Na2CrO4 solutions. It is based on the
principle that14 different solutions, when connected through
the vapor space, approach equilibrium by transferring solvent
due to the chemical potential gradients of the solvent in each
solution. At equilibrium, the chemical potentials of the solvent
in each solution are identical, which implies the equality of the
solvent activity.
Experiments were conducted in a slightly modified version
of the apparatus described by Zhou15 due to its favorable
reliability and a fairly fast rate of equilibration. The apparatus
mainly consisted of four small nickel cups for the reference
standard solution samples and one big nickel cup for the sample
being measured. The stock solution of Na2CrO4 and corre-
sponding CaCl2 reference standard solutions were prepared by
dissolving Na2CrO4 and CaCl2 reagents (both p.a. grade, Sigma-
Aldrich) in high-purity Milli-Q water. The weight of the sample
was precisely weighed, the mass of the sodium chromate
solution was approximately 85 g, and the corresponding
reference solutions were 1.0-1.5 g for each. Prior to each
measurement, air was removed from the apparatus with a
vacuum pump, and to prevent spattering of the solution during
evacuation, the apparatus was connected to an empty beaker
flask, which acted as an intermediate reservoir. Then the
apparatus was put on a rotating platform in a thermostatic water
bath at 353.15 K with a temperature precision of 0.1 K (SC-
30A, Ninbo Xinzhi), and the rotating speed was set to 40 rpm
to accelerate the equilibration.
The equilibrium was achieved when the differences between
the mass fractions of reference solutions were less than 1%,
and then the average of the molalities of the references was
reported. Besides, the initial and final molalities of the samples
and reference solutions were further analyzed by inductively
 Ind. Eng. Chem. Res., Vol. 49, No. 17, 2010 8245
Table 1. Experimental Osmotic Coefficients of NaOH-H2O and 1/2
AφI
Na2CrO4-H2O Systems and the Calculated Osmotic and Mean Ionic e-RI ) +
1/2
ΦNaOH ) 1 - + m(βNaOH
(0)
+ βNaOH
(1)
Activity Coefficients at 353.15 K 1 + bI 1/2

m CaCl2 m2CNaOH
φ
(2)
experiments (mol/kg) (mol/kg) Φexpt γ( Φcalc δ × 100 a

NaOH 0.50 0.3545 0.9030 0.9010 0.22 in which the ionic strength I is given as
1.00 0.6750 0.9222 0.9205 0.18

∑mz
3.00 1.7501 1.0560 1.0601 0.38 1
4.50 2.4802 1.1834 1.1828 0.05 I) i i
2
(3)
2
Na2CrO4 0.05 0.0483 0.8147 0.5007 0.8112 0.44
0.1 0.0930 0.7724 0.4187 0.7755 0.41
0.2 0.1783 0.7392 0.3412 0.7389 0.04 the Debye-Hückel parameter Aφ was taken as 0.4384 at 353.15
0.5 0.4030 0.6906 0.2502 0.6906 0.00 K calculated with Moller’s equation,17 b and R are the universal
0.8 0.6032 0.6749 0.2119 0.6740 0.14 parameters generally considered to be 1.2 (kg mol-1)1/2 and
1 0.7282 0.6721 0.1966 0.6723 0.04 2.0 (kg mol-1)1/2, respectively, the temperature-dependent Pitzer
1.2 0.8521 0.6766 0.1860 0.6762 0.07
1.5 1.0312 0.6868 0.1756 0.6897 0.42 parameters β(0) (1) φ
NaOH, βNaOH, and CNaOH were taken from Christov
18

2 1.3423 0.7287 0.1676 0.7277 0.14 as shown in Table 2, mi is the molality of species i in a
2.5 1.6584 0.7822 0.1671 0.7798 0.31 multicomponent solution, and zi is the valence of species i. The
3 1.9810 0.8435 0.1718 0.8426 0.11 relative average deviation between experimental and calculated
3.5 2.3152 0.9131 0.1811 0.9140 0.10
osmotic coefficients is 0.21%, indicating the apparatus and
4 2.6652 0.9918 0.1947 0.9930 0.12
4.5 3.0303 1.0777 0.2130 1.0788 0.20 method are significantly reliable. Consequently, the osmotic
5 3.4153 1.1724 0.2366 1.1709 0.13 coefficients of the Na2CrO4-H2O system at 353.15 K were
5.5 3.8023 1.2654 0.2665 1.2689 0.28 obtained and summarized in Table 1.
6 4.2292 1.3763 0.3039 1.3727 0.26 3.2. Correlation of the Na2CrO4-H2O System with
6.5 4.6541 1.4822 0.3508 1.4820 0.01
7 5.1038 1.5965 0.4095 1.5967 0.01
Pitzer Model. The experimental osmotic coefficients of
7.5 5.5720 1.7152 0.4831 1.7167 0.09 Na2CrO4-H2O were correlated with the Pitzer equation:
7.683 5.7551 1.7630 0.5145 1.7620 0.06
a
δ × 100 ) ((φcalc - φexpt)/(φexpt)) × 100. 2AφI1/2 4
e-RI ) +
1/2
ΦNa2CrO4 ) 1 - + m(βNa
(0)
2CrO4
+ βNa
(1)
2CrO4
Table 2. Pitzer Parameters of Aqueous Binary Systems at 353.15 K 1 + bI1/2 3
25/2 2 φ
solute β(0) β(1) Cφ m CNa2CrO4 (4)
3
CaCl2a 0.3204 1.7246 -0.0080
NaOHb 0.0984 0.1610 -0.0004 The obtained Pitzer parameters are presented in Table 2. The
Na2CrO4c 0.0784 1.2282 0.0052
calculated osmotic coefficients and their corresponding relative
a
The parameters of CaCl2 were correlated with the experimental data deviation are listed in Table 1; the comparison between the
of Anathaswamy.16 b The parameters of NaOH were taken from experimental and calculated osmotic coefficients of
Christov.18 c The parameter of Na2CrO4 were regressed by this work.
Na2CrO4-H2O system as a function of molality is illustrated
in Figure 1. The relative average deviation is 0.16% between
coupled atomic plasma emission spectrometry (ICP-AES, 2400 experimental and calculated values. It is obvious that the
type, Perkin-Elmer). experimental data are fully consistent with the correlated data,
indicating the Pitzer model is valid for such a system ranging
3. Results and Discussions from 0.05 to 7.683 m. Therefore, the mean ionic activity
coefficients of Na2CrO4 in pure water as a function of molality
3.1. Experimental Data. Results of the isopiestic molalities were calculated using the following Pitzer equation and
of the equilibration experiments at 353.15 K are listed in Table presented in Table 1 and Figure 2:
1. The experimental molality-based osmotic coefficient Φ of
test solution was obtained using the fundamental equation for
isopiestic equilibrium: ln γ(,Na2CrO4 ) -2Aφ ( I1/2
1 + bI 1/2
2
+ ln(1 + bI1/2) +
b )
{
(1)
βNa
Φ ) Φ*ν*m*/νm 4 2CrO4 1
(1)
3
(0)
m 2βNa 2CrO4
+2
R2I
[ (
1 - 1 + RI1/2 - R2I
2 ) ×

where Φ* is the osmotic coefficient of the reference solution
in isopiestic equilibrium with the test solution, ν* is the
stoichiometric coefficient of the reference solution, m* is the
molality of the reference solution, ν is the stoichiometric
coefficient of the test solution, and m is the molality of the test
solution. The reference osmotic coefficient of CaCl2 (mmax ) 6
m) was calculated with the Pitzer model, in which the Pitzer
parameters as shown in Table 2 are regressed from the
experimental osmotic coefficient values of Anathaswamy.16
To evaluate the reliability of our isopiestic apparatus, the
experimental osmotic coefficients of NaOH-H2O at 353.15 K
are also reported in Table 1. We compared the experimental
data with those calculated with the following Pitzer equation:
]} + 2
exp(-RI1/2) 3/2
m2CNa
φ
2CrO4
(5)
As can be seen in Figure 1 and Figure 2, as the concentration
increases, the osmotic and mean ionic activity coefficients
initially significantly decrease and then increase monotonically.
This phenomenon is consistent with other binary systems
observed, and it is due to the electrolyte-dependent complex
interaction among different ions and solvent. According to the
classical aqueous electrolyte solution theory,19 in dilute region,
as the concentration increases, the ion association is facilitated;
therefore the osmotic and activity coefficients are reduced. In
the concentrated region, the γ and Φ are mainly determined by
the hard sphere repulsive force; as the concentration increases,
8246 Ind. Eng. Chem. Res., Vol. 49, No. 17, 2010

Figure 1. Comparison between experimental and calculated osmotic

coefficient values using the Pitzer equation for Na2CrO4-H2O at 353.15
K.
Figure 3. Comparison between experimental and predicted solubility of
Na2CrO4 in NaOH-H2O at 353.15 K. (Experimental data were taken from
Zou.7)

Pitzer model, in which γ(, Na2CrO4 was obtained using the

following equation:

ln γ(,Na2CrO4 ) -2Aφ ( I1/2

1 + bI1/2
2
+ ln(1 + bI1/2) +
b )
4
m [B + (mNaOH + 2mNa2CrO4)CNaOH] +
3 NaOH NaOH
2 8
( m
3 NaOH 3 )
+ mNa2CrO4 [BNa2CrO4 + (mNaOH + 2mNa2CrO4) ×
CNa2CrO4] + mNaOH(mNaOH + 2mNa2CrO4) ×
4
Figure 2. Calculated mean ionic activity coefficients for Na2CrO4-H2O
( )
2B'NaOH + CNaOH + mNa2CrO4 ×
3
4
system using the Pitzer equation at 353.15 K.
(
(mNaOH + 2mNa2CrO4) 2B'Na2CrO4 + CNa2CrO4 (9)
3 )
the aggravating repulsive force among ions inhibits the ion
association, and therefore the γ and Φ increase. in which
3.3. Prediction of Na2CrO4 Solubility in Aqueous
(1)
NaOH Solutions at 353.15 K. A typical application of activity 2βMX
[1 - (1 + RI1/2)e-RI ]
1/2

coefficient models is to predict the solubility of a salt in an BMX(I) ) βMX

aqueous solution containing other salts. There are substantial
phase diagrams for the Na2CrO4-H2O20 and NaOH-Na2-
CrO4-H2O7,8,21 systems ranging from 298.15 to 383.15 K. At
353.15 K, the solubility of Na2CrO4 is 7.683 mol · kg-1 in the
Na2CrO4-H2O system, and the equilibrium solid phase is
Na2CrO4 in both the Na2CrO4-H2O and NaOH-Na2CrO4-
H2O systems. Therefore, the solid-liquid equilibrium is de-
scribed as follows:
Ksp
+ excess Gibbs free energy, respectively, zM is the cation valence,
Na2CrO4 798 2Na + CrO4 2-
The solubility productKsp,Na2CrO4 is expressed as
Ksp,Na2CrO4 ) (aNa+)2aCrO42- ) (mNa+)2mCrO42-(γ(,Na2CrO4)3 (7)
In our ternary system, the mNa+ is given by
mNa+ ) mNaOH + 2mNa2CrO4
From our experimental activity coefficient data for Na2CrO4
aqueous binary system, the Ksp,Na2CrO4 is 247.06 at 353.15 K
calculated using eq 7. Consequently, by employing the binary
Pitzer parameters in Table 2, the solubility of Na2CrO4 in
aqueous NaOH solutions at 353.15 K was predicted using the
(0)
+ (10)
RI2
φ
CMX
CMX ) (11)
2|zMzX | 1/2
B' )
∂B
(12)
∂I
BMX and CMX are the second and third virial coefficients in the
(6) and zX is the anion valence.
The comparison between experimental and predicted solubil-
ity is plotted in Figure 3. The deviations are relatively high,
and increased with an increase in the concentration of the
multicomponent solution. This result may be due to the relatively
large contribution of mixed ionic interaction in the
NaOH-Na2CrO4-H2O system. Because the Pitzer model is
applicable below 6 mol · kg-1, it is difficult for the Pitzer model
(8) to predict the solubility at higher concentration. The concentra-
tion level of our ternary system was much higher than 6
mol · kg-1. However, as can be seen in Figure 3, the predicted
values are consistent with the average relative deviation of
7.52% in the experimental values below a NaOH concentration
of 8.0 mol · kg-1, indicating a satisfactory prediction has been
achieved. As a whole, the application of the Pitzer equation to

predict the solubility of Na2CrO4 in aqueous NaOH solutions
at 353.15 K using binary parameters is considered to be
successful.
4. Conclusions
The osmotic coefficients of the Na2CrO4-H2O system at
353.15 K ranging from 0.05 to 7.683 mol · kg-1 were determined
with isopiestic method. The reliability of the data obtained was
validated by comparison with experimental results for NaOH
solutions from studies previously reported.
The experimental osmotic coefficients were excellently cor-
related with the Pitzer equation. Thus, the interaction parameters,
the mean ionic activity coefficients, and Ksp,Na2CrO4 were
obtained. Furthermore, the solubility of Na2CrO4 in NaOH
solutions at 353.15 K was predicted using binary parameters.
The predicted values are consistent with the average relative
deviation of 7.52% of the experimental values, demonstrating
the Pitzer equation is capable of optimizing the processes for
the removal and recovery of sodium chromate in NaOH
solutions at high temperature.
Acknowledgment
We express our great appreciation to Prof. Yigui Li as an
advisor on the electrolyte thermodynamics and to Prof. Jun Zhou
for the information and advice on the isopiestic apparatus.
Financial support from the National Basic Research Develop-
ment Program of China (973 Program) under Grant No.
2007CB613501, the National 863 Project of China under Grant
Nos. 2009AA064003 and 2006BAC02A05, and the National
Natural Science Foundation of China under Grant Nos. 50874099
and 50904057 is gratefully acknowledged.
Nomenclature
a ) activity
AΦ ) Debye-Hückel parameter
b ) closet approach parameter in the Debye-Hückel term
BMX ) second virial coefficient in the excess Gibbs free energy
CMX ) third virial coefficient in the excess Gibbs free energy
φ
CMX ) Pitzer ion-interaction parameter
I ) ionic strength
Ksp ) solubility product of solute in aqueous solutions
m ) molality of test solution at equilibrium (mol/kg H2O)
mi ) molality of species i (mol/kg H2O)
m* ) molality of reference solution at equilibrium (mol/kg H2O)
zi ) valence of species i
zM ) cation valence
zX ) anion valence
Greek Letters
R ) nonlinear parameter for second virial coefficient in the Pitzer
equation
(0)
βMX (1)
, βMX ) Pitzer ion-interaction parameters
γ( ) mean ionic activity coefficient
ν, ν* ) stoichiometric coefficient for the samples and reference
solution, respectively
φ, φ* ) osmotic coefficient for the test and reference solution,
respectively
Ind. Eng. Chem. Res., Vol. 49, No. 17, 2010 8247
Subscripts
M ) cation
X ) anion
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ReVised manuscript receiVed July 5, 2010
Accepted July 20, 2010
IE1011068